CN114586213A - Electrochemical device and electronic device - Google Patents
Electrochemical device and electronic device Download PDFInfo
- Publication number
- CN114586213A CN114586213A CN202180005827.XA CN202180005827A CN114586213A CN 114586213 A CN114586213 A CN 114586213A CN 202180005827 A CN202180005827 A CN 202180005827A CN 114586213 A CN114586213 A CN 114586213A
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- CN
- China
- Prior art keywords
- negative electrode
- electrochemical device
- active material
- material layer
- positive electrode
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides an electrochemical device and an electronic device, wherein the 0.2C discharge capacity of the electrochemical device at the temperature of minus 20 ℃ is A, the 0.2C discharge capacity of the electrochemical device at the temperature of 25 ℃ is B, and A/B is more than or equal to 70% and less than or equal to 90%. The electrochemical device provided by the embodiment of the application has good low-temperature charge and discharge performance at a low temperature of-20 ℃.
Description
Technical Field
The present application relates to the field of electrochemical energy storage, and more particularly to electrochemical devices and electronic devices.
Background
With the development and progress of electrochemical devices (e.g., lithium ion batteries), increasingly higher requirements are placed on low-temperature charge and discharge performance. At present, in order to improve the low-temperature charge and discharge performance of an electrochemical device, some measures have been taken to improve the performance, but the improvement has not been satisfactory.
Therefore, improvement of low-temperature charge and discharge performance of electrochemical devices remains a problem to be solved.
Disclosure of Invention
Some embodiments of the present application provide an electrochemical device having a 0.2C discharge capacity at-20 ℃ of A, a 0.2C discharge capacity at 25 ℃ of B, and 70% to A/B to 90%. In some embodiments, 71% ≦ A/B ≦ 87%. This shows that the electrochemical device provided in the embodiment of the present application has a good charge and discharge performance at a low temperature of-20 ℃, can charge and discharge more energy, and improves the satisfaction of the charge and discharge performance of the electrochemical device at a low temperature.
In some embodiments, the electrochemical device has a 0.2C discharge capacity of C at 45 ℃ of 103% C/B of 110%. The electrochemical device can charge and discharge more energy at medium and high temperature, and has better medium and high temperature charge and discharge performance.
In some embodiments, at least one of the following (a) or (b) is satisfied: (a) the electrochemical device comprises a negative electrode, and the thickness of the negative electrode is H when the electrochemical device is in a 50% charge state2When the electrochemical device is in a 0% charge state, the thickness of the negative electrode is H1，(H2-H1)/H1From 0% to 6%; (b) the electrochemical device comprises a negative electrode, and the thickness of the negative electrode is H when the electrochemical device is in a 100% charge state3When the electrochemical device is in a 0% charge state, the thickness of the negative electrode is H1，(H3-H1)/H1Is 0% to 8%. The thickness increase rate of the negative electrode when the electrochemical device is charged from 0% to 50% of the state of charge is shown, and the thickness increase rate of 0% to 6% shows that the negative electrode of the electrochemical device in the embodiment of the present application has less expansion during charging, which is beneficial to improving the charging and discharging performance of the electrochemical device.
In some embodiments, the electrochemical device includes a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer having a porosity of 20% to 50%, and optionally, the negative electrode active material layer having a porosity of 35% to 50%. If the porosity of the negative electrode active material layer is less than 20%, it means that the space between the negative electrode materials is small, which may result in insufficient contact between the negative electrode materials and the electrolyte, and thus the performance of the negative electrode cannot be fully exerted, and when the porosity of the negative electrode active material layer exceeds 50%, the electrical contact between the particles of the negative electrode materials may be poor due to the excessive gaps between the particles of the negative electrode materials, and the performance of the electrochemical device may be affected. In some embodiments, the porosity of the negative active material layer is 35% to 50%, in which case the performance of the electrochemical device is more excellent.
In some embodiments, the electrochemical device includes an anode including an anode current collector and an anode active material layer at the anode current collector, the anode active material layer including an anode material, the anode material including hard carbon, and satisfying at least one of the following (c) to (g): (c) the binding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 50N/m; preferably, the adhesion between the negative electrode active material layer and the negative electrode current collector is 10 to 48N/m;
(d) the compacted density of the negative electrode active material layer is 0.9g/cm3To 1.25g/cm3(ii) a (e) The particle breakage rate of the negative electrode material is 10-40%, and optionally, the particle breakage rate of the negative electrode material is 10-25%; (f) in an X-ray diffraction pattern of the negative electrode material, a diffraction peak is arranged between 18 degrees and 30 degrees, and the half-height peak width of the diffraction peak is 4 degrees to 10 degrees; (g) the interlayer spacing of the microcrystal sheets of the negative electrode material is 0.34-0.4 nm, optionally, the interlayer spacing of the microcrystal sheets of the negative electrode material is 0.37-0.39 nm, and optionally, the interlayer spacing of the microcrystal sheets of the negative electrode material is 0.37-0.38 nm.
The microcrystalline chip interlayer spacing of the negative electrode material is 0.37nm to 0.39nm, the dynamic performance of the negative electrode material is better, the expansion rate of the negative electrode is smaller, when the microcrystalline chip interlayer spacing of the negative electrode material is too small, the diffusion resistance of ions among microcrystalline chip layers is larger, and the microcrystalline chip layers are easily propped by the ions, so that the whole negative electrode is expanded. When the interlayer spacing of the microchip is too large, the situation of partial solvent co-intercalation may exist, the structure of the negative electrode material is damaged, and the overall electrical property is influenced.
In some embodiments, the electrochemical device satisfies at least one of the following (h) and (i): (h) the 1C discharge capacity of the electrochemical device at 25 ℃ is D, and D/B is more than 0.9 and less than 1; (i) the discharge capacity of the electrochemical device at 25 ℃ at 5C is E, and E/B is more than or equal to 99% and less than or equal to 105%. In some embodiments, the electrochemical device is monitored for a three-electrode potential, plotted on a voltage ordinate and a state of charge abscissa, with a negative delithiation curve in the ramp region at 0.3V to 0.8V and a negative delithiation curve below 0.2V having a state of charge fraction F of 30% to 80%. The negative pole delithiation curve is a slope region from 0.3V to 0.8V (the slope region means that the included angle between the electrochemical curve and a 0V horizontal line is more than 30 degrees, namely, compared with an initial curve, the included angle is obvious rising trend), and the charge state occupation ratio F of the negative pole delithiation curve below 0.2V is from 30% to 80%. In some embodiments, the slope region is an intrinsic characteristic of the hard carbon material, the delithiation curves of different anode materials are different at the soc ratio F below 0.2V, the dynamic performance of the electrochemical device is better when the soc ratio F below 0.2V is 30% to 80%, but if the soc ratio F below 0.2V is greater than 80%, the overall voltage of the electrochemical device is lower and the energy density is reduced.
In some embodiments, the electrochemical device comprises a positive electrode comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid, and a negative electrode comprising a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the single-sided positive electrode active material layer per unit area having a weight M1The weight of the single-sided negative electrode active material layer per unit area is M2，M1/M2Is 2 to 6. In some embodiments, the electrochemical device has a CB value of 0.9 to 1.1, optionally, a CB value of 0.95 to 1.06; wherein, the CB value is the ratio of the negative electrode capacity to the positive electrode capacity in the same area. That is, CB is the negative electrode capacity/positive electrode capacity, and the negative electrode capacity is CWNegative electrodeX g capacityNegative electrodeX percentage of active materialNegative electrodeThe capacity of the positive electrode is ═CWPositive electrodeX g capacityPositive electrodeX percentage of active materialPositive electrode. Percentage of active materialPositive electrodeAnd percent active materialNegative electrodeThe mass ratio of the positive electrode material to the positive electrode active material layer and the mass ratio of the negative electrode material to the negative electrode active material layer are respectively expressed. By setting the CB value, the performances of the anode material and the cathode material can be fully exerted, the anode material and the hard carbon material reasonably matched with the cathode material can cause too many lithium ions provided by the anode and cause lithium precipitation of the cathode when the CB value is too small when an electrochemical device is a lithium ion battery, and the energy density can be reduced when the CB value is too large.
The present application also provides an electronic device comprising the electrochemical device of any one of the above.
In the examples of the present application, the electrochemical device had a discharge capacity at-20 ℃ of 0.2C of B, and the electrochemical device had a discharge capacity at 25 ℃ of 0.2C of 70% to 90% A/B. The electrochemical device provided by the embodiment of the application has good low-temperature charge and discharge performance at the low temperature of-20 ℃, and can charge and discharge more energy.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present application and are not intended to limit the present application in any way.
Electrochemical devices, such as lithium ion batteries, are widely used in various fields, and have a wide range of applications. At low temperatures, the charge and discharge performance of electrochemical devices is often unsatisfactory, and further improvement is desired.
In the description of the present disclosure, "100% state of charge" refers to a state in which the electrochemical device is charged to a maximum design voltage by constant current, and includes a state after standing (typically, standing for 10min), all considered as a full charge state, unless otherwise specified, the maximum design voltage includes, but is not limited to, 4.48V, 4.5V, 4.53V, or 4.45V, and even higher.
In the description of the present disclosure, "0% state of charge" refers to a state in which the electrochemical device is discharged at a constant current to a minimum design voltage, and includes a state after standing (typically, standing for 10min), all considered as a fully discharged state, unless otherwise specified, and the maximum design voltage includes, but is not limited to, 3.0V, 2.8V, 2.6V, or 2.0V, and even lower. Similarly, in the description of the present disclosure, the 50% state of charge includes a state after standing (typically, standing for 10 min).
Some embodiments of the present application provide an electrochemical device having a discharge capacity A at-20 ℃ of 0.2C, a discharge capacity B at 25 ℃ of 0.2C, and an A/B ratio of 70% to 90%. In some embodiments, the discharge capacity B of the electrochemical device at 0.2C at 25 ℃ represents the charge and discharge performance of the electrochemical device at normal temperature, the discharge capacity A of the electrochemical device at 0.2C at-20 ℃ represents the charge and discharge performance of the electrochemical device at low temperature, and the A/B represents the retention rate of the charge and discharge performance of the electrochemical device at low temperature, wherein the A/B is more than or equal to 70% and less than or equal to 90%, which indicates that the electrochemical device provided in the embodiments of the present application has better charge and discharge performance at low temperature of-20 ℃, can charge and discharge more energy, and improves the satisfaction degree of the charge and discharge performance of the electrochemical device at low temperature.
In some embodiments of the present application, the electrochemical device has a 0.2C discharge capacity of C at 45 ℃ of 103% C/B of 110%. In some embodiments, the 0.2C discharge capacity at 45 ℃ of the electrochemical device is C, which characterizes the charge-discharge performance of the electrochemical device at medium and high temperatures, and the C/B of 103% to 110% indicates that the electrochemical device can charge and discharge more energy at medium and high temperatures, and has better medium and high temperature charge-discharge performance.
In some embodiments of the present application, the electrochemical device comprises a negative electrode having a thickness H at 50% state of charge2The thickness of the negative electrode of the electrochemical device at 0% state of charge is H1，(H2-H1)/H1Is 0% to 6%. In some embodiments, (H)2-H1)/H1The thickness increase rate of the negative electrode when the electrochemical device is charged from 0% to 50% of the charge state is shown, and the thickness increase rate of 0% to 6% shows that the negative electrode of the electrochemical device in the embodiment of the present application has less expansion during the charging process, which is beneficial to improvingHigh charge and discharge performance of electrochemical device.
In some embodiments of the present application, the electrochemical device comprises a negative electrode having a thickness H at 100% state of charge3The thickness of the negative electrode of the electrochemical device at 0% state of charge is H1，(H3-H1)/H1Is 0% to 8%. In some embodiments, (H)3-H1)/H1The thickness growth rate of the negative electrode when the electrochemical device is charged from 0% to 100% of the state of charge is shown, and the thickness growth rate of 0% to 8% shows that the negative electrode of the electrochemical device in the embodiment of the present application has less expansion in the whole charging process, which is beneficial to improving the charging and discharging performance of the electrochemical device.
In some embodiments of the present application, an electrochemical device includes a negative electrode including a negative electrode current collector and a negative electrode active material layer at the negative electrode current collector, the negative electrode active material layer having a porosity of 20% to 50%. In some embodiments, if the porosity of the negative electrode active material layer is less than 20%, it means that the space between the negative electrode materials is small, which may result in insufficient contact between the negative electrode materials and the electrolyte, and thus the performance of the negative electrode may not be fully exerted, and when the porosity of the negative electrode active material layer exceeds 50%, the gaps between the particles of the negative electrode materials may be too large, which may result in poor electrical contact between the particles of the negative electrode materials, and thus the performance of the electrochemical device may be affected. In some embodiments, the porosity of the negative active material layer is 35% to 50%, in which case the performance of the electrochemical device is more excellent.
Porosity test of the negative active material layer:
and taking the fully placed lithium ion battery, disassembling, taking out the negative electrode, soaking the negative electrode for 20min by using DMC (ethylene carbonate), cleaning the negative electrode by using DMC and acetone in sequence, placing the negative electrode in an oven, and drying the negative electrode for 12h at the temperature of 80 ℃. Grinding the anode ions to prepare a sample, observing the sample under an SEM, respectively cutting ten SEM pictures of the section containing the first active material layer and the section containing the second active material layer, wherein the area of the SEM pictures is A20 mu m multiplied by 20 mu m, and the section of the whole anode is the SEM picture, calculating the area B of the pore at the darker part in the section by using image processing software (multiple), wherein the porosity is B/A multiplied by 100%, and then calculating the average value of the porosities of the ten SEM pictures, namely the porosity of the anode active material layer.
In some embodiments of the present application, the electrochemical device includes a negative electrode including a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer including a negative electrode material, the negative electrode material including hard carbon, and a cohesive force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 50N/m. In some embodiments, if the adhesion between the negative active material layer and the negative current collector is too small, peeling or poor contact between the negative active material layer and the negative current collector during charge and discharge of the electrochemical device may be caused, which is not favorable for electron conduction and affects the test performance. If the adhesion between the negative electrode active material layer and the negative electrode current collector is too large, it may be necessary to use too much binder, which may be detrimental to the electrical conductivity of the negative electrode, affecting the kinetic performance.
Testing the binding power of the negative active material layer and the negative current collector:
the brand of an instrument used for testing the adhesive force between the negative active material layer and the negative current collector is Instron, the model is 33652, a negative electrode (with the width of 30mm multiplied by the length (100mm to 160mm)) is taken and fixed on a steel plate by using double-sided adhesive paper (with the model: 3M9448A, the width of 20mm multiplied by the length (90mm to 150mm)), a paper tape with the same width as the negative electrode is fixed with one side of the negative electrode by using the adhesive paper, a limiting block of a tensile machine is adjusted to a proper position, the paper tape is folded and slid upwards for 40mm, the sliding speed is 50mm/min, and the adhesive force between the negative active material layer and the negative current collector under 180 degrees (namely, the negative current collector is stretched in the opposite direction) is tested.
In some embodiments of the present application, the compacted density of the negative active material layer is 0.9g/cm3To 1.25g/cm3. Test of compacted density of negative electrode active material layer:
taking a lithium ion battery which is completely discharged, disassembling a negative electrode, cleaning, drying, weighing the negative electrode (the two sides of a negative electrode current collector are coated with negative electrode active material layers) with a certain area S by using an electronic balance, recording the weight as W1, and measuring the thickness T1 of the negative electrode by using a ten-thousandth micrometer. The negative active material layer was washed off using a solvent, dried, and the weight of the negative current collector was measured as W2, and the thickness of the negative current collector, T2, was measured using a ten-thousandth ruler. The weight W0 and the thickness T0 of the negative electrode active material layer provided on the negative electrode current collector side and the compacted density of the negative electrode active material layer were calculated by the following formulas:
W0＝(W1-W2)/2
T0＝(T1-T2)/2
the compacted density is W0/(T0 × S).
In some embodiments, if the compaction density of the negative active material layer is too low, it is not favorable for the volumetric energy density of the electrochemical device and also for the conduction of electrons in the negative active material layer. If the compaction density of the negative electrode active material layer is too high, the electrolyte may not sufficiently infiltrate the negative electrode active material layer, which is not favorable for sufficiently exerting the performance of the negative electrode.
In some embodiments of the present application, the anode material has a particle breakage rate of 10% to 40%, in some embodiments, the particle breakage rate of the anode material is a ratio of broken particles of the anode material to the total number of particles of the anode material, in the case of counting the particle breakage rate of the negative electrode material, the negative electrode active material layer may be photographed using a Scanning Electron Microscope (SEM), at least 10 regions of a predetermined area (10 μm × 10 μm) may be selected, and by counting the total number of particles in each predetermined area, then counting the number of the broken particles in the preset area, wherein the particle breakage rate of the negative electrode material is the number of the broken particles/the total number of the particles, the broken particles are visible cracks, namely, the gap between the two parts which can be completely overlapped shows that the particles are broken, when the total particle number is counted, the particles with the particle diameter larger than 3 mu m are counted, and the particle breakage rate of the cathode material in the regions is counted. The negative pole of electrochemical device can lead to the fact the granule part of negative pole material to be broken through the roll-in usually in manufacturing process, and the granule breakage of a small amount of negative pole material is favorable to increasing the area of contact with electrolyte, improves multiplying power performance, if the granule breakage rate of negative pole material is too high, will excessively increase the consumption of electrolyte, and is optional, and the granule breakage rate of negative pole material is 10% to 25%, and electrochemical device's wholeness can be better this moment.
In some embodiments of the present application, the anode material has an X-ray diffraction pattern having a diffraction peak between 18 ° and 30 °, and the half height peak width of the diffraction peak is 4 ° to 10 °. In some embodiments, there is only one diffraction peak between 18 ° and 30 ° with a full width at half maximum of 4 ° to 10 °, and in some embodiments, the negative electrode material may include hard carbon.
In some embodiments of the present application, the anode material has a microchip interlayer spacing of 0.34nm to 0.4 nm. In some embodiments, the anode material comprises a carbon material, and a crystallite interlayer spacing of 0.34nm to 0.4nm indicates that the carbon material is amorphous carbon. Optionally, the inter-layer distance of the micro-crystal plates of the negative electrode material is 0.38nm to 0.39nm, the dynamic performance of the negative electrode material is better, the expansion rate of the negative electrode is smaller, when the inter-layer distance of the micro-crystal plates of the negative electrode material is too small, the diffusion resistance of ions between the micro-crystal plate layers is larger, and the micro-crystal plate layers are easily propped by the ions, so that the overall expansion of the negative electrode is caused. When the interlayer spacing of the microchip is too large, the situation of partial solvent co-intercalation may exist, the structure of the negative electrode material is damaged, and the overall electrical property is influenced.
In some embodiments of the present application, the electrochemical device has a discharge capacity D at 25 ℃ of 1C, 0.9< D/B < 1. In some embodiments, the charge and discharge performance at 1C rate of the electrochemical device is nearly unchanged compared to the charge and discharge performance at 0.2C, and the electrochemical device has good rate performance.
In some embodiments of the present application, the electrochemical device has a 5C discharge capacity E at 25 ℃ of 99% E/B of 105%. In some embodiments, the electrochemical device has a discharge capacity at 5C rate greater than 0.2C at a temperature of 25 ℃, indicating that the electrochemical device has good high-rate charge and discharge performance.
In some embodiments, the electrochemical device is monitored for a three-electrode potential, and the negative delithiation curve is a ramp region at 0.3V to 0.8V (ramp region means that the electrochemical curve is more than 30 ° from the 0V horizontal line, i.e., a significant upward trend compared to the initial curve) and the negative delithiation curve is 30% to 80% below 0.2V in state of charge versus F, plotted with voltage as ordinate and state of charge as abscissa. In some embodiments, the slope region is an intrinsic characteristic of the hard carbon material, the delithiation curves of different anode materials are different at the soc ratio F below 0.2V, the dynamic performance of the electrochemical device is better when the soc ratio F below 0.2V is 30% to 80%, but if the soc ratio F below 0.2V is greater than 80%, the overall voltage of the electrochemical device is lower and the energy density is reduced.
In some embodiments, the electrochemical device comprises a positive electrode comprising a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid, and a negative electrode comprising a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the single-sided positive electrode active material layer per unit area having a weight M1The weight of the single-sided negative electrode active material layer per unit area is M2，M1/M2Is 2 to 6. In some embodiments, one or both sides of the positive electrode current collector may have a positive electrode active material layer, M1The weight of the positive electrode active material layer per unit area on one side of the positive electrode current collector, and similarly, the negative electrode current collector having the negative electrode active material layer on one or both sides thereof, M2Is the weight of the negative active material layer per unit area on one side of the negative current collector.
In some embodiments, the electrochemical device has a CB value of 0.9 to 1.1, optionally, a CB value of 0.95 to 1.06; wherein, the CB value is the ratio of the negative electrode capacity to the positive electrode capacity in the same area. In some embodiments, by setting the CB value, the performance of the positive electrode material and the negative electrode material can be fully exerted, and no waste is caused, when the CB value is too small, in the case of a lithium ion battery, too many lithium ions may be supplied from the positive electrode, causing lithium precipitation from the negative electrode, and when the CB value is too large, the energy density may be reduced. Wherein CB is a negative electrode capacity/positive electrode capacity, and the negative electrode capacity is (CW)Negative electrodeX g capacityNegative electrodeX percentage of active materialNegative electrode) The positive electrode has a Capacity of (CW)Positive electrodeX g capacityPositive electrodeX percentage of active materialPositive electrode) The said CWNegative electrodeAnd CWPositive electrodeFor coating, 1540.25mm was weighed2The weight of the negative electrode active material layer and the weight of the positive electrode active material layer over an area, whereinThe percentage of CW and active material is obtained by removing the cell to form a positive and negative electrode and punching small disks (e.g., 1540.25 mm) over the flat positive and negative electrodes, respectively2Area), and the weight of the active material layer is weighed to be CW (weight of coating film area-weight of bare copper aluminum foil). And then adding concentrated hydrochloric acid to the small round piece for digestion, filtering, drying, and calculating the percentage of the active material in the active material layer (the weight of the object to be measured after hydrochloric acid digestion and drying/the weight of the object to be measured before hydrochloric acid digestion).
Gram volumeNegative electrodeAnd grammage ofPositive electrodeAnd (3) testing:
the first step is as follows: manufacturing a button-type battery: cutting a negative electrode (positive electrode) into a wafer with the diameter phi (diameter) of 14mm serving as a working electrode, taking metal lithium with the diameter phi of 18mm as a counter electrode and a reference electrode, separating the counter electrode and the reference electrode by a PE (polyethylene) isolating membrane with the diameter phi of 20mm, dropwise adding a proper amount of the electrolyte, and assembling to obtain the CR2430 type button cell.
The second step is that: and (3) gram capacity test: and taking the assembled button cell to ensure that the Open Circuit Voltage (OCV) is normal, wherein each group at least comprises 4 parallel samples. The voltage window of the button cell is set between 0V and 2.5V. Standing for 1h at 25 ℃, then discharging the battery with three-stage low current of 0.05C/50uA/20 muA, enabling an SEI (solid electrolyte interface film) to form a film on a negative electrode and recording the lithium intercalation capacity (enabling a film to be formed on a positive electrode and recording the lithium intercalation capacity). The cell was then charged to 2.5V at 0.1C and the negative (positive) delithiation capacity, i.e. the gram capacity of the negative material (positive material), was recordedNegative electrode(gram volume)Positive electrode)。
The anode material in some embodiments of the present application includes a carbon material, and the following briefly describes a preparation process of the anode material to better understand the present application, but this is only exemplary and not intended to limit the present application. Dissolving raw material 1 (such as phenolic resin) in solvent 1 (such as ethanol), stirring for a period of time to obtain a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃, cooling to a temperature, taking out a solid part, and drying. And sintering the material in a box furnace according to a certain sintering mode to obtain the cathode material. In some embodiments, solvent 1 may also be: water, acetone, methanol, dichloromethane, ethyl acetate, hexane, petroleum ether, toluene or N-methylpyrrolidone. In some embodiments, when the starting material 1 is a soluble material, it may be: epoxy resins, urea resins, amino resins, ether resins, polyester resins, sucrose or glucose. When the raw material 1 is an insoluble material, the sintering step can be directly performed, and the raw material 1 comprises: biomass such as hull, straw and the like, lignocellulose, starch, polyvinyl chloride, polyethylene, polypropylene, polystyrene ABS plastic and the like. It is to be understood that this method of preparation is exemplary only and that other suitable methods of preparation may also be employed. In some embodiments, an electrochemical device using the anode material proposed in the present application has excellent low-temperature charge and discharge properties, large rate properties, and a small expansion ratio.
In some embodiments, a conductive agent and a binder may also be included in the negative active material layer. In some embodiments, the conductive agent in the negative active material layer may include at least one of conductive carbon black, ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers. In some embodiments, the binder in the negative active material layer may include at least one of carboxymethyl cellulose (CMC), polyacrylic acid, polyvinyl pyrrolidone, polyaniline, polyimide, polyamideimide, polysiloxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin, or polyfluorene. In some embodiments, the mass ratio of the anode material, the conductive agent, and the binder in the anode active material layer may be (78 to 98.5): (0.1 to 10). The negative electrode material may be a mixture of a silicon-based material and other materials. It will be appreciated that the above description is merely exemplary and that any other suitable materials and mass ratios may be employed. In some embodiments, the negative electrode current collector may employ at least one of a copper foil, a nickel foil, or a carbon-based current collector.
In some embodiments, the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer may include a positive electrode material. The positive electrode material includes a positive electrode material capable of absorbing and releasing lithium (Li). Examples of the positive electrode material capable of absorbing/releasing lithium may include lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium iron phosphate, lithium titanate, and lithium-rich manganese-based materials.
Specifically, the chemical formula of lithium cobaltate may be as shown in chemical formula 1:
LixCoaM1bO2-cchemical formula 1
Wherein M1 represents at least one selected from the group consisting of nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), yttrium (Y), lanthanum (La), zirconium (Zr), and silicon (Si), and x, a, B, and c values are respectively in the following ranges: x is more than or equal to 0.8 and less than or equal to 1.2, a is more than or equal to 0.8 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 0.2, and c is more than or equal to-0.1 and less than or equal to 0.2;
the chemical formula of lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate can be as shown in chemical formula 2:
LiyNidM2eO2-fchemical formula 2
Wherein M2 represents at least one selected from the group consisting of cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr), and silicon (Si), and y, d, e, and f are respectively in the following ranges: y is more than or equal to 0.8 and less than or equal to 1.2, d is more than or equal to 0.3 and less than or equal to 0.98, e is more than or equal to 0.02 and less than or equal to 0.7, f is more than or equal to 0.1 and less than or equal to 0.2:
the chemical formula of lithium manganate can be as chemical formula 3:
LizMn2-gM3gO4-hchemical formula 3
Wherein M3 represents at least one selected from the group consisting of cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), and z, g, and h values are respectively in the following ranges: z is more than or equal to 0.8 and less than or equal to 1.2, g is more than or equal to 0 and less than 1.0, and h is more than or equal to-0.2 and less than or equal to 0.2.
In some embodiments, the positive electrode active material layer may further include a conductive agent. In some embodiments, the conductive agent in the positive electrode active material layer may include at least one of conductive carbon black, ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers. In some embodiments, the positive electrode active material layer may further include a binder, and the binder in the positive electrode active material layer may include at least one of carboxymethyl cellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysiloxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin, or polyfluorene. In some embodiments, the mass ratio of the cathode material, the conductive agent, and the binder in the cathode active material layer may be (80 to 99): (0.1 to 10). In some embodiments, the thickness of the positive electrode active material layer may be 10 μm to 500 μm. It should be understood that the above description is merely an example, and any other suitable material, thickness, and mass ratio may be employed for the positive electrode active material layer. In some embodiments, the positive current collector of the positive electrode may be an Al foil, but of course, other current collectors commonly used in the art may be used. In some embodiments, the thickness of the positive current collector of the positive electrode may be 1 μm to 50 μm. In some embodiments, the positive electrode active material layer may be coated only on a partial area of the positive electrode collector.
In some embodiments, the electrochemical device includes a separator disposed between the positive electrode and the negative electrode. The isolation film comprises at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide or aramid. For example, the polyethylene includes at least one selected from high density polyethylene, low density polyethylene, or ultra high molecular weight polyethylene. Particularly polyethylene and polypropylene, which have a good effect on preventing short circuits and can improve the stability of the battery through a shutdown effect. In some embodiments, the thickness of the isolation film is in the range of about 5 μm to 50 μm.
In some embodiments, the surface of the separator may further include a porous layer disposed on at least one surface of the separator, the porous layer including inorganic particles selected from alumina (Al) and a binder2O3) Silicon oxide (SiO)2) Magnesium oxide (MgO), titanium oxide (TiO)2) Hafnium oxide (HfO)2) Tin oxide (SnO)2)、Cerium oxide (CeO)2) Nickel oxide (NiO), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO)2) Yttrium oxide (Y)2O3) At least one of silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or barium sulfate. In some embodiments, the pores of the separator film have a diameter in the range of about 0.01 μm to 1 μm. The binder of the porous layer is at least one selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene. The porous layer on the surface of the isolating membrane can improve the heat resistance, the oxidation resistance and the electrolyte infiltration performance of the isolating membrane and enhance the adhesion between the isolating membrane and the pole piece.
In some embodiments of the present application, the electrochemical device is of a rolled, stacked or folded type. In some embodiments, the positive electrode and/or the negative electrode of the electrochemical device may be a multilayer structure formed by winding or stacking, or may be a single-layer structure in which a single-layer positive electrode, a single-layer negative electrode, and a separator are stacked.
In some embodiments, the electrochemical device comprises a lithium ion battery, but the application is not so limited. In some embodiments, the electrochemical device may further include an electrolyte. The electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolytic solution including a lithium salt and a non-aqueous solvent. The lithium salt is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6One or more of LiBOB or lithium difluoroborate. For example, LiPF is selected as lithium salt6Because it has high ionic conductivity and can improve cycle characteristics. The non-aqueous solvent may be a carbonate compound, an ester-based compound, an ether-based compound, a ketone-based compound, an alcohol-based compound, a,An aprotic solvent, or a combination thereof. The carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluoro carbonate compound, or a combination thereof.
Examples of the chain carbonate compound are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Methyl Ethyl Carbonate (MEC), and combinations thereof. Examples of the cyclic carbonate compound are Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), Vinyl Ethylene Carbonate (VEC), or a combination thereof. Examples of the fluoro carbonate compound are fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1, 2, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof.
Examples of carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ -butyrolactone, decalactone, valerolactone, mevalonic lactone, caprolactone, methyl formate, or combinations thereof.
Examples of the ether compound are dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or a combination thereof.
Examples of other organic solvents are dimethylsulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters or combinations thereof.
In some embodiments of the present application, taking a lithium ion battery as an example, a positive electrode, a separator, and a negative electrode are sequentially wound or stacked to form an electrode member, and then are packaged in, for example, an aluminum plastic film, and an electrolyte is injected, formed, and packaged to form the lithium ion battery. And then, performing performance test on the prepared lithium ion battery.
Those skilled in the art will appreciate that the above-described methods of making electrochemical devices (e.g., lithium ion batteries) are merely examples. Other methods commonly used in the art may be employed without departing from the disclosure herein.
Embodiments of the present application also provide an electronic device including the electrochemical device described above. The electronic device of the embodiment of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile, a portable copier, a portable printer, a head-mounted stereo headset, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic notebook, a calculator, a memory card, a portable recorder, a radio, a backup power source, an electric motor, an automobile, a motorcycle, a power-assisted bicycle, a drone, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large household battery, a lithium ion capacitor, and the like.
In the following, some specific examples and comparative examples are listed to better illustrate the present application, wherein a lithium ion battery is taken as an example.
Example 1
Preparation of the positive electrode: mixing lithium cobaltate, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to the weight ratio of 97.5: 1.0: 1.5, adding N-methylpyrrolidone (NMP) as a solvent, and uniformly stirring. And uniformly coating the slurry on an aluminum foil of a positive current collector, wherein the coating thickness is 80 mu m, and drying, cold pressing and cutting to obtain the positive electrode.
Preparation of a negative electrode: dissolving epoxy resin in ethanol, stirring for a period of time to obtain a mixed solution, adding a curing agent (m-phenylenediamine) (the mass ratio of the epoxy resin to the curing agent is 10: 1), transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃, cooling to the temperature, and taking out a solid part. And placing the mixture into a box furnace, heating to 200 ℃ at the speed of 5 ℃/min under the condition of introducing nitrogen, keeping the temperature for 1h, then heating to 900 ℃ at the speed of 5 ℃/min for 2h, naturally cooling, and crushing to obtain the cathode material. Dissolving a negative electrode material, conductive carbon black and styrene butadiene rubber or modified PAA in deionized water according to the weight ratio of 96: 1.5: 2.5 to form negative electrode slurry. And (2) adopting a copper foil with the thickness of 6 micrometers as a current collector of the negative electrode, coating the negative electrode slurry on the current collector of the negative electrode, wherein the thickness of the coated negative electrode active material layer is 50 micrometers, drying, cold pressing (rolling) under the conditions of pressure of 30 tons and roller gap of 100 micrometers, and cutting to obtain the negative electrode, wherein the porosity of the obtained negative electrode active material layer is 30%.
Preparing an isolating membrane: the separator was 7 μm thick Polyethylene (PE).
Preparing an electrolyte: under the environment that the water content is less than 10ppm, LiPF6Adding a non-aqueous organic solvent, wherein the non-aqueous organic solvent comprises EC, PC and DEC, and the mass ratio of the three organic solvents is as follows: ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC) 2: 6, LiPF6The concentration of (A) is 1.15mol/L, and the electrolyte is obtained after uniform mixing.
Preparing a lithium ion battery: and sequentially stacking the anode, the isolating membrane and the cathode in sequence to enable the isolating membrane to be positioned between the anode and the cathode to play an isolating role, and winding to obtain the electrode assembly. And (3) placing the electrode assembly in an outer packaging aluminum-plastic film, dehydrating at 80 ℃, injecting the electrolyte, packaging, and performing technological processes such as formation, degassing, edge cutting and the like to obtain the lithium ion battery.
The 6 μm thickness of the copper foil means a smaller resistance than the typical 8 μm to 16 μm thickness of the copper foil, and in combination with the hard carbon material in the present application, a large rate of charge and discharge can be achieved and a higher energy density is achieved.
In other examples and comparative examples, parameters were changed in addition to the procedure of example 1, and specific changed parameters are shown in the following table.
The following describes a method of testing various parameters of the present application.
1) Testing of high and Low temperature Performance
Discharging the battery to 3V at constant current in an environment of 25 ℃, performing first charging and discharging, performing constant current and constant voltage charging at a charging current of 0.7C until the upper limit voltage is 4.48V, then performing constant current discharging at a discharging current of 0.2C until the final voltage is 3V, and recording the discharging capacity B at 25 ℃; then, constant current and constant voltage charging was repeated at a charging current of 0.7C until the upper limit voltage was 4.48V, the temperature was adjusted to-20℃, and then constant current discharging was performed at a discharging current of 0.2C until the final voltage was 3V, at which time the discharging capacity a at-20℃ was recorded. The temperature was adjusted to 25 ℃, constant current and constant voltage charging was carried out at a charging current of 0.7 ℃ until the upper limit voltage was 4.48V, then the temperature was adjusted to 45 ℃, constant current discharging was carried out at a discharging current of 0.2 ℃ until the final voltage was 3V, at which time the discharging capacity C at 45 ℃ was recorded.
The low-temperature capacity retention ratio A/B (25 ℃ discharge capacity B/-20 ℃ discharge capacity A) × 100%
High-temperature capacity retention rate C/B ═ discharge capacity C at 45 ℃ C/discharge capacity B at 25 ℃ X100%
2) Test of Rate Properties
Discharging the battery to 3V at constant current in an environment of 25 ℃, performing first charging and discharging, performing constant current and constant voltage charging under a charging current of 0.7C until the upper limit voltage is 4.48V, performing constant current discharging under a discharging current of 0.2C until the final voltage is 3V, recording the discharging capacity of 0.2C, repeating constant current and constant voltage charging under a charging current of 0.7C until the upper limit voltage is 4.48V, setting the discharging multiplying factor to be 1C and 5C in sequence, performing constant current discharging until the final voltage is 3V, and recording the discharging capacity of 1C and 5C
Capacity retention ratio D/B of 1C ═ (discharge capacity at 0.2C/discharge capacity at 1C) × 100%
Capacity retention rate E/B of 5C ═ (discharge capacity at 0.2C/discharge capacity at 5C) × 100%
The difference between examples 2 to 8 in table 1 and example 1 is that the ratio of the curing agent and the epoxy resin was adjusted so that the mass ratio of the epoxy resin and the curing agent (m-phenylenediamine) was between 1: 1 and 10: 1, respectively, and the material crystallite interlayer spacing was achieved as shown in table 1 by the control of the rolling pressure, and a suitable porosity of the anode active material layer was obtained.
Table 1 shows the respective parameters and evaluation results of examples 1 to 8 and comparative examples 1 to 2.
Note: h1Is 0% of the thickness of the negative electrode of the electrochemical device in the charged state, H2Is the thickness of the negative electrode of an electrochemical device at 50% state of charge, H3Is the negative electrode thickness of the electrochemical device at 100% state of charge.
Referring to table 1, it can be seen from comparison of examples 1 to 5 in table 1 that the a/B value of the electrochemical device increases and the cyclic expansion decreases as the microcrystalline interlayer distance of the anode material increases. It can be seen that the microcrystalline interlayer spacing of the negative electrode material has an influence on the low-temperature charging performance of the electrochemical device, and when the microcrystalline layer of the material is small, the performance of the negative electrode material is damaged, mainly because the electrolyte ion transmission is slow under a low-temperature condition, and on the basis, the small microcrystalline interlayer spacing increases the transmission resistance of lithium ions, which leads to large expansion of the negative electrode material. The crystallite spacing of the negative electrode is not preferably larger than 0.4nm, because when the crystallite layer spacing of the negative electrode material is too large, part of solvent in the electrolyte may be co-embedded into the negative electrode material, so that the structure of the negative electrode material is damaged, and the overall electrical performance of the electrochemical device is influenced. Meanwhile, C/B is relatively sensitive to the lamella spacing of the material, and the material has poor lithium intercalation kinetics under the condition that the low lamella spacing causes the increase of lithium intercalation resistance, and is easy to generate structural damage in the lithium intercalation process at high temperature, so that the material is unfavorable. Comparative example 2 the resistance and polarization caused by the excessively small pitch of the lower layer at low temperature were extremely large, resulting in a decrease in low temperature performance.
As can be seen by comparing examples 6 to 8 in table 1, as the porosity of the negative active material layer increases, the a/B of the cell increases first and then decreases. The reason is that when the porosity is too small, the electrolyte is not infiltrated sufficiently, the material is easy to precipitate lithium at low temperature, along with the increase of the porosity, the contact between the electrolyte and the material is more sufficient, the lithium intercalation and lithium deintercalation distance is shortened, and the dynamic performance of the material is improved. However, in the process of increasing, the comparative example 1 has a poor low temperature performance compared to example 1, although the C/B ratio is improved to some extent.
In table 2, examples 9 to 12, the change of the adhesive force was controlled by the change of the amount of the binder of PAA (polyacrylic acid), the ratio of PAA was controlled to be 2.8% to 6%, and the adhesive force between the active material and the current collector was increased as the ratio of PAA was increased. The breakage of the pellets of examples 13 to 15 was caused by the rolling change at the cold pressing, and the rolling pressure used was 30 to 50 tons, and the rolling pressure used in comparative examples 3 to 4 was 60 tons or more.
Table 2 shows the respective parameters and evaluation results of example 4 and examples 9 to 15 and comparative examples 3 to 4.
Referring to table 2, when the adhesion is adjusted on the basis of example 4, and the particle breakage rate is maintained at a low level as the adhesion between the negative active material layer and the negative current collector is increased in examples 9 to 12, the low-temperature capacity retention rate of the electrochemical device is maintained at a stable level, and the capacity retention rates at 1C rate and 5C rate are decreased. This is because, when the adhesion between the negative active material layer and the negative current collector is too large, the content of the binder of the negative electrode is too high, the binder is not a non-conductor, the electron conductivity is reduced while the migration of lithium ions is hindered, the internal resistance of the electrode sheet is increased, and the kinetic performance of the negative electrode material is affected, thereby causing a decrease in the capacity retention ratio at 1C magnification and 5C magnification of the electrochemical device. However, the binding force cannot be too small, as in comparative example 3, there may be a case where the negative electrode active material layer is peeled off from the negative electrode current collector due to the small binding force, resulting in an increase in internal resistance and a decrease in rate performance.
Referring to table 2, the negative electrode particle breakage rate is adjusted on the basis of example 4, in examples 13 to 15, the rate performance is hindered by adjusting the particle breakage rate of the negative electrode material, polarization is further aggravated by impedance increase and SEI thickening due to further influence of an electrical contact network between particles caused by breakage, current unevenness and lithium precipitation are easily caused, the particles are separated from a current collector, and the capacity retention rate D/B at 1C rate and the capacity retention rate E/B at 5C rate are reduced along with the increase of the breakage rate. Therefore, the particle breakage rate of the anode material needs to be controlled to be lower than 40%, the comparative example 4 has higher breakage rate, and the overall rate performance of the material is poor.
Table 3 shows the respective parameters and evaluation results of examples 16 to 22.
Referring to table 3, in examples 16 to 19, the CB value is adjusted and adjusted on the basis of example 4, and it can be seen that, as the CB value decreases, the low-temperature capacity retention rate of the electrochemical device and the capacity retention rate at 1C, 5C rate have a process of first changing little and then decreasing, and the CB change decreases fastest from 0.95 to 0.9. This is because the negative electrode materials of examples 16 to 19 belong to hard carbon materials, and the hard carbon materials have a certain over-intercalation ability, so when the CB value is 0.95, the negative electrode materials can still normally operate, and thus obtain a relatively large energy density, but when the CB value is less than 0.95, the negative electrode materials precipitate lithium due to too many lithium ions provided by the positive electrode, and the low temperature performance and the rate performance are affected, and when the CB value exceeds 1.1, the energy density of the electrochemical device is reduced due to too large CB value, and the anode potential is raised, so that the cathode potential is forced to be raised, and the electrical performance is not favorably exerted.
Referring to Table 3, M was adjusted on the basis of example 41/M2As can be seen from examples 17 to 21, the weight M of the single-sided positive electrode active material layer per unit area1Weight M of negative electrode active material layer per unit area2The increase of the ratio of (a) reduces the low-temperature capacity retention rate of the electrochemical device, and also reduces the capacity retention rates at 1C rate and 5C rate. This is because with M1/M2The dynamic performance of the anode material is poor, so that the overall dynamic performance of electrochemistry is influenced, and further, the capacity retention rate under 1C multiplying power and 5C multiplying power is influenced. Therefore, during design, reasonable matching needs to be performed according to the capacities of the negative electrode material and the positive electrode material, so that the M of the cell design1/M2Within the preferred ranges.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the disclosure herein is not limited to the particular combination of features described above, but also encompasses other combinations of features described above or equivalents thereof. For example, the above features and the technical features having similar functions disclosed in the present application are mutually replaced to form the technical solution.
Claims (10)
1. An electrochemical device, characterized in that,
the discharge capacity of the electrochemical device at-20 ℃ is A at 0.2C, the discharge capacity of the electrochemical device at 25 ℃ at 0.2C is B, and A/B is more than or equal to 70% and less than or equal to 90%.
2. The electrochemical device of claim 1, wherein the electrochemical device has a 0.2C discharge capacity of C, 103% ≦ C/B ≦ 110% at 45 ℃.
3. The electrochemical device according to claim 1, wherein at least one of the following (a) or (b) is satisfied:
(a) the electrochemical device comprises a negative electrode, and the thickness of the negative electrode is H when the electrochemical device is in a 50% charge state2When the electrochemical device is in a 0% charge state, the thickness of the negative electrode is H1，(H2-H1)/H1From 0% to 6%;
(b) the electrochemical device comprises a negative electrode, and the thickness of the negative electrode is H when the electrochemical device is in a 100% charge state3When the electrochemical device is in a 0% charge state, the thickness of the negative electrode is H1，(H3-H1)/H1Is 0% to 8%.
4. The electrochemical device according to claim 1, wherein the electrochemical device comprises a negative electrode including a negative electrode current collector and a negative electrode active material layer at the negative electrode current collector, and a porosity of the negative electrode active material layer is 20% to 50%.
5. The electrochemical device according to claim 1, wherein the electrochemical device comprises a negative electrode including a negative electrode current collector and a negative electrode active material layer at the negative electrode current collector, the negative electrode active material layer including a negative electrode material including hard carbon, and satisfying at least one of the following (c) to (g):
(c) the binding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 50N/m;
(d) the compacted density of the negative electrode active material layer is 0.9g/cm3To 1.25g/cm3；
(e) The particle breakage rate of the anode material is 10% to 40%;
(f) in an X-ray diffraction pattern of the negative electrode material, a diffraction peak is arranged between 18 degrees and 30 degrees, and the half-height peak width of the diffraction peak is 4 degrees to 10 degrees;
(g) the microcrystalline chip interlayer distance of the negative electrode material is 0.34 nm-0.4 nm.
6. The electrochemical device according to claim 1, wherein at least one of the following (h) or (i) is satisfied:
(h) the 1C discharge capacity of the electrochemical device at 25 ℃ is D, and 0.9< D/B < 1;
(i) the 5C discharge capacity of the electrochemical device at 25 ℃ is E, and E/B is more than or equal to 99% and less than or equal to 105%.
7. The electrochemical device of claim 1, wherein said electrochemical device is monitored for a three-electrode potential, and wherein said three-electrode potential is plotted on a voltage ordinate and a state of charge abscissa, wherein said negative delithiation curve is in a ramp region at 0.3V to 0.8V, and wherein said negative delithiation curve has a state of charge fraction F below 0.2V of 30% to 80%.
8. The electrochemical device according to claim 1, wherein the electrochemical device comprises a positive electrode and a negative electrode, the positive electrode comprises a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid, the negative electrode comprises a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, and the weight of the positive electrode active material layer per unit area on one surface is M1The weight of the negative electrode active material layer per unit area is M2，M1/M2Is 2 to 6.
9. The electrochemical device according to claim 1, wherein the electrochemical device has a CB value of 0.9 to 1.1;
wherein, CB is negative electrode capacity/positive electrode capacity, and the negative electrode capacity is CWNegative electrodeX g capacityNegative electrodeX percentage of active materialNegative electrodeThe positive electrode capacity is CWPositive electrodeX g capacityPositive electrodeX percentage of active materialPositive electrode。
10. An electronic device comprising the electrochemical device according to any one of claims 1 to 9.
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